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Operando vibrational spectroscopic measurements at metalloenzyme-modified electrodes toward developments of bio-inspired electrocatalysts

Research Project

Project/Area Number 19H02664
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 32010:Fundamental physical chemistry-related
Research InstitutionHokkaido University

Principal Investigator

Yagi Ichizo  北海道大学, 地球環境科学研究院, 教授 (40292776)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥17,030,000 (Direct Cost: ¥13,100,000、Indirect Cost: ¥3,930,000)
Fiscal Year 2021: ¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000)
Fiscal Year 2020: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
Fiscal Year 2019: ¥9,100,000 (Direct Cost: ¥7,000,000、Indirect Cost: ¥2,100,000)
Keywords金属酵素 / 脂質二重膜 / 一酸化窒素還元酵素 / チトクロムc酸化酵素 / 電極触媒反応 / 表面増強赤外吸収分光法 / 人工生体膜モデル / 表面増強赤外分光法 / 膜蛋白質 / チトクロムc / 酸素還元反応 / 生体模倣電極触媒 / 表面増強振動分光 / 自己組織化膜 / 振動和周波発生分光法 / テラヘルツラマン散乱分光法 / 蛋白質電気化学 / 金属酵素修飾電極 / オペランド計測 / 界面振動分光 / 多電子多プロトン移動 / 一酸化炭素還元酵素 / 表面増強赤外吸収分光 / テラヘルツラマン散乱分光 / 振動和周波発生分光
Outline of Research at the Start

生体内の金属酵素は、従来の人工触媒では到達できない高効率で多電子多プロトン移動反応を駆動している。本研究では、電極表面に金属酵素を配置し、電位制御により活性中心を活性化/不活性化させながら、特徴的な3つの振動分光法を駆使して、金属酵素の活性中心(コア)と活性中心周辺のアミノ酸鎖(シェル)の構造、シェル内の水和構造、吸着した反応物・中間体・生成物などの動的な濃度・構造変化を追跡し、酵素の優れた触媒活性を模倣する上で必要な要素を探索する。

Outline of Final Research Achievements

To design bio-inspired electrocatalysts, metalloenzymes were buried in the artificial bilayer lipid membrane (BLM) systems constructed on electrode surfaces combined with surface enhanced infrared absorption (SEIRA) spectroscopy. The targets are the cytochrome c-dependent nitric oxide reductase (cNOR) in the denitrification system and cytochrome c oxidase (CcO) in the respiration chain. Enzyme reactions at the both systems were monitored by electrochemical vibrational spectroscopic measurements.
At the cNOR system, the orientation of the fixed enzymes were controlled by changing the ratio of end groups and chain lengths of the self-assembled monolayer on the electrode surfaces. Furthermore, the more stable BLMs were constructed, enabling us to observe the intermediate NO vibrational bands during the reaction. At the CcO system, the effect of the adsorption of cytochrome c on CcO was evaluated.

Academic Significance and Societal Importance of the Research Achievements

金属酵素などの活性中心を模倣する生体模倣電極触媒は、従来、白金等の遷移金属ベースで発展してきた燃料電池電極触媒や硝酸還元触媒の限界を打ち破る触媒設計指針として研究されてきた。しかしながら、反応時の金属酵素の活性中心の反応中間体吸着構造やその周辺の配位構造の影響については未だ未解明であり、今回SEIRA活性基板上に構築した人工生体膜モデルで反応を駆動しながら、酵素の内部構造や反応中間体を捉える手法が確立できた。特にcNORは、地球温暖化ガスとして注目されている亜酸化窒素(N2O)を生成する反応であり、その生成機構を解明し、抑制することにつながるため、社会的にも意義のある研究につながった。

Report

(4 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • Research Products

    (21 results)

All 2022 2021 2020 2019 Other

All Journal Article (6 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 5 results,  Open Access: 1 results) Presentation (13 results) (of which Int'l Joint Research: 5 results,  Invited: 3 results) Remarks (2 results)

  • [Journal Article] <i>In situ</i> X-ray Absorption Spectroscopy at Platinum Group Metal (PGM) and Non-PGM Electrocatalysts2022

    • Author(s)
      加藤優、八木一三
    • Journal Title

      Denki Kagaku

      Volume: 90 Issue: 1 Pages: 16-20

    • DOI

      10.5796/denkikagaku.22-FE0005

    • ISSN
      2433-3255, 2433-3263
    • Year and Date
      2022-03-05
    • Related Report
      2021 Annual Research Report
  • [Journal Article] Impact of membrane protein-lipid interactions on formation of bilayer lipid membranes on SAM-modified gold electrode2021

    • Author(s)
      Kato Masaru、Masuda Yuya、Yoshida Narumi、Tosha Takehiko、Shiro Yoshitsugu、Yagi Ichizo
    • Journal Title

      Electrochimica Acta

      Volume: 373 Pages: 137888-137888

    • DOI

      10.1016/j.electacta.2021.137888

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Impact of Heterometallic Cooperativity of Iron and Copper Active Sites on Electrocatalytic Oxygen Reduction Kinetics2021

    • Author(s)
      Masaru Kato, Natsuki Fujibayashi, Daiki Abe, Naohiro Matsubara, Satoshi Yasuda, Ichizo Yagi
    • Journal Title

      ACS Catalyst

      Volume: 11 Issue: 4 Pages: 2356-2365

    • DOI

      10.1021/acscatal.0c04753

    • NAID

      120007193351

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Electrocatalytic activity and volatile product selectivity for nitrate reduction at tin-modified Pt(100), Pd(100) and Pd?Pt(100) single crystal electrodes in acidic media2021

    • Author(s)
      Kato Masaru、Unuma Yuki、Okui Manabu、Qu Yunteng、Zheng Jinhang、Taguchi Satoshi、Kiguchi Fumiya、Torihata Mashu、Gao Yunzhi、Hoshi Nagahiro、Yagi Ichizo
    • Journal Title

      Electrochimica Acta

      Volume: 398 Pages: 139281-139281

    • DOI

      10.1016/j.electacta.2021.139281

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Electrocatalytic Oxygen Reduction at Multinuclear Metal Active Sites Inspired by Metalloenzymes2020

    • Author(s)
      Masaru Kato and Ichizo Yagi
    • Journal Title

      e-Journal of Surface Science and Nanotechnology

      Volume: 18 Issue: 0 Pages: 81-93

    • DOI

      10.1380/ejssnt.2020.81

    • NAID

      130007808461

    • ISSN
      1348-0391
    • Year and Date
      2020-03-14
    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Terahertz Raman Spectroscopy of Ligand-Protected Au8 Clusters2020

    • Author(s)
      Masaru Kato*, Yukatsu Shichibu, Kazuya Ogura, Mitsuhiro Iwasaki, Mizuho Sugiuchi, Katsuaki Konishi, and Ichizo Yagi*
    • Journal Title

      The Journal of Physical Chemistry Letters

      Volume: 11 Issue: 19 Pages: 7996-8001

    • DOI

      10.1021/acs.jpclett.0c02227

    • NAID

      120007160303

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Presentation] 脂質膜修飾電極界面におけるタンパク質会合挙動の追跡2022

    • Author(s)
      佐野綾哉、吉田生未、加藤優、八木一三
    • Organizer
      化学系学協会北海道支部2021年冬季研究発表会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 酸素還元反応に対する鉄と銅サイトの異種金属協働効果2021

    • Author(s)
      加藤優、藤林那月、阿部大輝、保田諭、八木一三
    • Organizer
      第128回触媒討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 金属酵素活性中心に倣った非白金系電極触媒の酸素還元能2021

    • Author(s)
      八木一三
    • Organizer
      2021年電気化学会秋季大会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] シトクロムc酸化酵素修飾電極における擬似生体膜の構築およびシトクロムc会合のその場観察2021

    • Author(s)
      佐野綾哉、吉田生未、加藤優、八木一三
    • Organizer
      2021年表面真空学会学術講演会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Electrochemical Surface-Enhanced Infrared Absorption Spectroscopy of Nitric Oxide Reductase Immobilized on Gold Electrodes2020

    • Author(s)
      Ichizo YAGI, Yuya MASUDA, Narumi YOSHIDA, Shogo NAKAGAWA, Takehiko TOSHA, Masaru KATO
    • Organizer
      71st Annual Meeting of International Society of Electrochemistry (ISE)
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] SAM-Au 電極における金属酵素吸着過程と脂質膜構築のその場観察2020

    • Author(s)
      吉田生未,鳴海旭,増田侑也,當舎武彦,加藤優,八木一三
    • Organizer
      2020年度日本表面真空学会学術講演会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 金属微粒子を含まない(Cu,Fe)ーNドープカーボン触媒の酸素還元活性2020

    • Author(s)
      阿部大輝, 藤林那月, 加藤優, 保田諭, 八木一三
    • Organizer
      第61回電池討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Mechanistic Insights into Enzymatic Nitric Oxide Reduction Revealed By Surface-Enhanced Infrared Absorption Spectroscopy Absorption Spectroscopy2019

    • Author(s)
      Kato Masaru, Masuda Yuya, Nakagawa Shogo, Tosha Takehiko, Yagi Ichizo
    • Organizer
      235th ECS Meeting
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Surface-Enhanced Infrared Absorption Spectroscopy of Nitric Oxide Reductase Immobilized on Gold Electrodes2019

    • Author(s)
      Kato Masaru, Masuda Yuya, Nakagawa Shogo, Tosha Takehiko, Yagi Ichizo
    • Organizer
      ISABC15
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Operando Monitoring of Nitric Oxide Reduction at Enzyme- Modified Electrode by ATR-SEIRA Spectroscopy2019

    • Author(s)
      Yagi Ichizo, Masuda Yuya, Nakagawa Shogo, Tosha Takehiko, Kato Masaru
    • Organizer
      ICAVS 10
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 種々の計測で解き明かす電極触媒活性の向上2019

    • Author(s)
      八木一三
    • Organizer
      電気化学会関西支部・東海支部合同シンポジウム
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] NonPGM Electrocatalysts for Oxygen Reduction Reaction Inspired By Metalloenzyme Active Sites2019

    • Author(s)
      Kato Masaru, Fujibayashi Natsuki, Matsubara Naohiro, Muto Marika, Murotani Takeshi, Yagi Ichizo
    • Organizer
      236th ECS Meeting
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 酸素還元活性に対するカーボンナノチューブへの銅ー鉄共ドーピング効果2019

    • Author(s)
      藤林那月、松原直啓、加藤優、保田諭、八木一三
    • Organizer
      電気化学会第87回大会
    • Related Report
      2019 Annual Research Report
  • [Remarks] 生体分子固定電極におけるその場計測

    • URL

      https://iyagilab.jp/home-jp/portfolio/project-title-3

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report 2019 Annual Research Report
  • [Remarks] 酵素模倣多電子移動電極触媒

    • URL

      https://iyagilab.jp/home-jp/portfolio/project-title

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report

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Published: 2019-04-18   Modified: 2023-01-30  

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